At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organ...At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.展开更多
基金supported by National Natural Science Foundation of China (Nos. 22274039 and 22178089)Hunan Provincial Innovation Foundation for Postgraduate (No.CX20220392)。
文摘At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.
